Phosphorus removal from municipal wastewater by hydrous ferric oxide reactive filtration and coupled chemically enhanced secondary treatment: part II--mechanism.

The removal mechanism of a hydrous ferric oxide (HFO) reactive filtration (RF) process with coupled chemically enhanced secondary treatment (RECYCLE) for phosphorus removal from municipal wastewater (HFO-RF-RECYCLE) was examined. A 0.95-ML/d (0.25-mgd) demonstration of HFO-RF-RECYCLE was performed at a municipal wastewater treatment plant equipped with oxidation ditches and secondary clarifiers. Influent to the plant averaged 6.0 mg/L phosphorus, with a 3-month tertiary effluent average of 0.011 mg/L phosphorus. In addition to aqueous geochemical modeling, experiments with surface charge, scanning electron microscopy, adsorptive capacity, thermal desorption, and most probable number of iron(III)-reducing bacteria were performed on samples from the system, to determine the major phosphorus-removal pathways. Results suggest that, in addition to filtration of particulate phosphorus, the low tertiary effluent total phosphorus result was achieved by adsorption.     

Groundwater flow, multicomponent transport and biogeochemistry: development and application of a coupled process model

A research tool for modeling the reactive flow and transport of groundwater contaminants in multiple dimensions is presented. Arbitrarily complex coupled kinetic–equilibrium heterogeneous reaction networks, automatic code generation, transfer-function based solutions, parameter estimation, high-resolution methods for advection, and robust solvers for the mixed kinetic–equilibrium chemistry are some of the features of reactive flow and transport (RAFT) that make it a versatile research tool in the modeling of a wide variety of laboratory and field experiments. The treatment of reactions is quite general so that RAFT can be used to model biological, adsorption/desorption, complexation, and mineral dissolution/precipitation reactions among others. The integrated framework involving automated code generation and parameter estimation allows for the development, characterization, and evaluation of mechanistic process models. The model is described and used to solve a problem in competitive adsorption that illustrates some of these features. The model is also used to study the development of an in situ Fe(II)-zone by encouraging the growth of an iron-reducing bacterium with lactate as the electron donor. Such redox barriers are effective in sequestering groundwater contaminants such as chromate and TCE.     

Evaluating the sensitivity of a subsurface multicomponent reactive transport model with respect to transport and reaction parameters.

The input variables for a numerical model of reactive solute transport in groundwater include both transport parameters, such as hydraulic conductivity and infiltration, and reaction parameters that describe the important chemical and biological processes in the system. These parameters are subject to uncertainty due to measurement error and due to the spatial variability of properties in the subsurface environment. This paper compares the relative effects of uncertainty in the transport and reaction parameters on the results of a solute transport model. This question is addressed by comparing the magnitudes of the local sensitivity coefficients for transport and reaction parameters. General sensitivity equations are presented for transport parameters, reaction parameters, and the initial (background) concentrations in the problem domain. Parameter sensitivity coefficients are then calculated for an example problem in which uranium(VI) hydrolysis species are transported through a two-dimensional domain with a spatially variable pattern of surface complexation sites. In this example, the reaction model includes equilibrium speciation reactions and mass transfer-limited non-electrostatic surface complexation reactions. The set of parameters to which the model is most sensitive includes the initial concentration of one of the surface sites, the formation constant (Kf) of one of the surface complexes and the hydraulic conductivity within the reactive zone. For this example problem, the sensitivity analysis demonstrates that transport and reaction parameters are equally important in terms of how their variability affects the model results.     

Hydrous ferric oxide nanoparticles hosted porous polyethersulfone adsorptive membrane: chromium (VI) adsorptive studies and its applicability for water/wastewater treatment

In this present study, adsorptive membranes for Cr(VI) ion removal were prepared by blending polyethersulfone (PES) with hydrous ferric oxide (HFO) nanoparticles (NPs). The effects of HFO NPs to PES weight ratio (0–1.5) on the physicochemical properties of the resultant HFO/PES adsorptive membranes were investigated with respect to the surface chemistry and roughness as well as structural morphologies using different analytical instruments. The adsorptive performance of the HFO NPs/PES membranes was studied via batch adsorption experiments under various conditions by varying solution pH, initial concentration of Cr(VI), and contact time. The results showed that the membrane made of HFO/PES at a weight ratio of 1.0 exhibited the highest adsorption capacity which is 13.5 mg/g. Isotherm and kinetic studies revealed that the mechanism is best fitted to the Langmuir model and pseudo-second-order model. For filtration of Cr(VI), the best promising membranes showed improved water flux (629.3 L/m² h) with Cr(VI) ion removal of 75%. More importantly, the newly developed membrane maintained the Cr(VI) concentration below the maximum contamination level (MCL) for up to 9 h.

     

铁屑法处理活性染料废水的实验研究

研究了反应时间、染料浓度、进水pH以及不同的废铸铁屑投加量的条件下，废铸铁屑内电解法处理模拟印染废水的脱色能力。并采用铁屑滤床强化厌氧一好氧膜生物反应器（A／OMBR）处理含活性染料的模拟废水。研究结果表明，铁屑对模拟印染废水的最佳脱色时间为12min，酸性条件下铁屑的脱色率优于碱性条件．随铁屑投加量的增加，系统对印染废水的脱色率提高，铁屑滤床强化A／OMBR处理可以提高组合工艺出水色度和COD的去除率。     

Significance of design and operational variables in chemical phosphorus removal

Batch and continuous experiments using model and real wastewaters were conducted to investigate the effect of metal salt (ferric and alum) addition in wastewater treatment and the corresponding phosphate removal from a design and operational perspective. Key factors expected to influence the phosphorus removal efficiency, such as pH, alkalinity, metal dose, metal type, initial and residual phosphate concentration, mixing, reaction time, age of flocs, and organic content of wastewater, were investigated. The lowest achievable concentration of orthophosphate under optimal conditions (0.01 to 0.05 mg/L) was similar for both aluminum and iron salts, with a broad optimum pH range of 5.0 to 7.0. Thus, in the typical operating range of wastewater treatment plants, pH is not a sensitive indicator of phosphorus removal efficiency. The most significant effect for engineering practice, apart from the metal dose, is that of mixing intensity and slow kinetic removal of phosphorus in contact with the chemical sludge formed. Experiments show that significant savings in chemical cost could be achieved by vigorously mixing the added chemical at the point of dosage and, if conditions allow, providing a longer contact time between the metal hydroxide flocs and the phosphate content of the wastewater. These conditions promoted the achievement of less than 0.1 mg/L residual orthophosphate content, even at lower metal-to-phosphorus molar ratios. These observations are consistent with the surface complexation model presented in a companion paper (Smith et al., 2008).     

Redox reactions in the Fe-As-O2 system

We have examined two redox reactions involving arsenic and iron at near-neutral pH: the reduction of As(V) by Fe(II) under anoxic conditions, and the co-oxidation of As(III) during Fe(II) oxygenation. We also considered the impact of goethite, pH buffers, and radical scavengers on these reactions. In a series of anoxic experiments, Fe(II) was found to reduce As(V) in the presence of goethite, but not in homogeneous solution. The reaction rate increased with increasing pH and Fe(II) concentration, but in all cases was relatively slow. In aerobic experiments, the kinetics of Fe(II) oxygenation at neutral pH, and the corresponding oxidation of As(III) were found to depend heavily on pH buffer type and concentration. The classic formulation of Fe(II) oxidation by oxygen, involving four single-electron transfers, was reviewed and found to be inadequate for explaining observed oxidation of Fe(II) and As(III). Widely cited rate constants for Fe(II) oxygenation originate from experiments conducted in carbonate buffer, and do not match observations made in phosphate, MES, or HEPES systems. In phosphate buffer, Fe(II) oxidation is rapid and dependent on phosphate concentration. In MES and HEPES buffers, Fe(II) oxidation is much slower due to the lack of labile ferrous iron species. Oxygenation of Fe(II) appears to proceed through different mechanisms in phosphate and MES or HEPES systems. In both cases, reactive intermediary species are produced which can oxidize As(III). These oxidants are not the hydroxyl radical, but may be Fe(IV) species.     

Geochemical modeling of cadmium sorption to soil as a function of soil properties

Cadmium sorption experiments were conducted to infer Cd sorption mechanisms to a reference smectite and three fractions of a Vertisol soil. Untreated Vertisol has a higher adsorption capacity for Cd than that of reference smectite. Surface complex modeling was used to calculate the potential contributions of Cd complexation reactions with permanent charge sites and pH-dependent charge sites over ranges in pH, for soils with given surface areas, and sorption site densities. The Langmuir model produced relatively good predictions of Cd sorption on reference smectite and Vertisol. However, the results of the triple-layer model (TLM) were inadequate to describe Cd adsorption on fixed-charge sites because the model could not account for the ion-exchange reaction on the basal plane. Based upon the two geochemical models of Cd adsorption to the reference smectite and Vertisol, it appears that the basal plane siloxane cavities are the most important sites for Cd complexation at pH < 6.5. For the pH-dependent sites, the edge-site aluminol appears to be the dominant surface functional group responsible for Cd adsorption at pH > 6.5.     

Regeneration of iron for trichloroethylene reduction by Shewanella alga BrY

Zero valent iron (ZVI), the primary reactive material in several permeable reactive barriers, is often oxidized to ferrous or ferric iron, resulting in decreased reactivity with time. Iron reducing bacteria can reconvert the ferric iron to its ferrous form, prolonging the reduction of chlorinated organic contaminants. In this study, the reduction of Fe(II,III) oxide and Fe(III) oxide by a strain of iron reducing bacteria of the group Shewanella alga BrY(S. alga BrY) was observed in both aqueous and solid phases. S. alga BrY preferentially reduced dissolved ferric iron over the solid ferric iron. In the presence of iron oxide the Fe(II) ions reduced by S. alga BrY efficiently reduced trichloroethylene (TCE). On the other hand, Fe(II) produced by S. alga BrY covered the reactive surfaces of ZVI iron filings and inhibited the reduction of TCE by ZVI. The formation of precipitates on the iron oxide or Fe0 surface was confirmed by scanning electron microscopy. The results suggest that iron-reducing bacteria in the oxidized Fe0 barriers can enhance the removal rate of chlorinated organic compounds and influence on the long-term performance of Fe0 reactive barriers.     

Retention of Cd, Zn and Co on hydroxyapatite filters

This study qualifies and quantifies the immobilization of Cd, Zn and Co, (used as models of bivalent metal ions due to their relevant toxicity) in filters of synthetic hydroxyapatite (HAP) [Ca5(PO4)3OH]. They were flushed with solutions containing Cd (1 x 10(-5)M), Zn and Co (1 x 10(-4)M) at constant pH (8.6) and ionic strength (0.01 M). The concentration of these metal ions in the outlet was measured by ICP-OEM spectroscopy. The software PHREEQC (version 2.4.2) was used to model sorption process and the potential effect of salinity (KCl), pH, alkalinity (NaHCO3) and hardness (CaCl2) over the efficiency of the treatment. Results showed an excellent retention capacity of HAP for Cd, Zn and Co. Sorption data were successfully described considering a mix model of surface complexation onto phosphate surface groups, ionic exchange in surface calcium sites and the precipitation of ZnO. Co exchange and surface complexation constants (Kex and Kc) were taken from previous experiments, while KexCd=0.32 and KcCd=0.63 were estimated from our modeling results. Predictive values of metal ion sorption show that: (a) an increase in hardness does not play a significant role in the retention capacity of these metals on HAP; (b) an increase in alkalinity promotes the precipitation of MeCO3 which could alter the hydrodynamic of the column; (c) a decrease in pH and an increase in salinity inhibit ZnO precipitation enhancing Zn and Cd adsorption and decreasing Co retention on HAP.     

Surface complexation modeling of Yb(III) sorption and desorption on hematite and alumina

Sorption and desorption of Yb(III) were studied on hematite and on alumina using a surface complexation model. The experimental methodology was conceived to allow an analysis of the data using a constant capacitance model. The FITEQL code was used for the calculations.The experimental results tend to show reversibility of sorption when the surface loading is small, and irreversibility when the surface loading is high. Surface complexation modeling gives a good interpretation of these two phenomena, taking into account hydroxylation of the surface complexes. In these two cases, it is possible to describe sorption and desorption curves with the same surface stoichiometries and the same surface complexation constants. The existence of these surface complexes depends on the pH of the solution, surface loading, and reaction direction.     

Quantification and modelling of 2,4-dinitrotoluene reduction with high-purity and cast iron

Cast iron has been used as a reactive material in permeable reactive barriers (PRBs) for site remediation. While reactions are generally believed to occur on the iron (oxide) surface, a recent study by [Oh, S.Y., Cha, D.K., Chiu, P.C., 2002a. Graphite-mediated reduction of 2,4-dinitrotoluene with elemental iron. Environ. Sci. Technol. 36 (10), 2178-2184] showed that graphite inclusions in cast iron can also serve as reaction sites for 2,4-dinitrotoluene (DNT). These authors also found that graphite-mediated reduction of DNT has a regioselectivity that is different from that for iron surface. In this study, we quantified the observations reported by Oh et al. and examined the role of graphite in cast iron through numerical modelling. Models containing one and two reaction sites were developed to evaluate the mass transfer, sorption and reaction rates for DNT reduction in batch systems containing high-purity and cast iron. Our simulations showed that the regioselectivity, defined as the ratio of the ortho- and para-nitro reduction rate constants, was 0.37+/-0.04 S.E. (S.E.=one estimated standard error) for iron surface and 3.59+/-0.76 S.E. for graphite surface. In the cast iron-water system, we estimated that at least 66+/-2% S.E. of the DNT was reduced on graphite surface, despite the low graphite content and the lower DNT reduction rate with graphite than with iron. Graphite played such an important role because of the rapid adsorption of DNT to graphite. In the batch experiments conducted by Oh et al., external mass transfer was not rate limiting. Surface reaction was the rate-limiting step for DNT reduction on the graphite surface in cast iron, whereas internal mass transfer and/or adsorption and surface reaction were important for high-purity iron.     

Competitive complexation of metal ions with humic substances

The surface complexation model was applied to simulate the competitive complexation of Ni, Ca and Al with humic substances. The presence of two types of binding sites in humic acid, carboxylic and phenolic functional groups, were assumed at both low and high pH conditions. Potentiometric titrations were used to characterize the intrinsic acidity constants of the two binding sites and their concentrations. It was found that the diffuse-layer model (DLM) could fit the experimental data well under different experimental conditions. Ni and Ca ions strongly compete with each other for reactions with the humic acid but Al showed little influence on the complexation of either Ni or Ca due to its hydrolysis and precipitation at pH approximately 5. The surface complexation constants determined from the mono-element systems were compared with those obtained from the multiple-element system (a mixture of the three metal ions). Results indicate little changes in the intrinsic surface complexation constants. Modeling results also indicate that high concentrations of Ca in the contaminated groundwater could strongly inhibit the complexation of Ni ions whereas an increase in pH and the humic concentration could attenuate such competitive interactions. The present study suggests that the surface complexation model could be useful in predicting interactions of the metal ions with humic substances and potentially aid in the design of remediation strategies for metal-contaminated soil and groundwater.     

RES3T-Rossendorf expert system for surface and sorption thermodynamics

This paper presents a digitized version of a thermodynamic sorption database, implemented as a relational database with MS Access. It is mineral-specific and can therefore be used for additive models of complex solid phases such as rocks or soils. An integrated user interface helps users to access selected mineral and sorption data, to extract internally consistent data sets for sorption modeling, and to export them in formats suitable for other modeling software. Data records comprise mineral properties, specific surface area values, surface binding sites' characteristics, sorption ligand information, and surface complexation reactions. An extensive bibliography is included, providing links not only to the above listed data, but also to background information concerning surface complexation model theories, evidence for surface species, and sorption experimental techniques.     

REST-Rossendorf expert system for surface and sorption thermodynamics

This paper presents a digitized version of a thermodynamic sorption database, implemented as a relational database with MS Access. It is mineral-specific and can therefore be used for additive models of complex solid phases such as rocks or soils. An integrated user interface helps users to access selected mineral and sorption data, to extract internally consistent data sets for sorption modeling, and to export them in formats suitable for other modeling software. Data records comprise mineral properties, specific surface area values, surface binding sites' characteristics, sorption ligand information, and surface complexation reactions. An extensive bibliography is included, providing links not only to the above listed data, but also to background information concerning surface complexation model theories, evidence for surface species, and sorption experimental techniques.     

Modeling the competitive effect of phosphate, sulfate, silicate, and tungstate anions on the adsorption of molybdate onto goethite

The mobility of Mo in soils and sediments depends on several factors including soil mineralogy and the presence of other oxyanions that compete with Mo for the adsorbent's retention sites. Batch experiments addressing Mo adsorption onto goethite were conducted with phosphate, sulfate, silicate, and tungstate as competing anions in order to produce competitive two anions adsorption envelopes, as well as competitive two anions adsorption isotherms. Tungstate and phosphate appear to be the strongest competitors of Mo for the adsorption sites of goethite, whereas little competitive effects were observed in the case of silicate and sulfate. Mo adsorption isotherm from a phosphate solution was similar to the one from a tungstate solution. The charge distribution multi-site complexation (CD-MUSIC) model was used to predict competitive adsorption between MoO(4)(2-) and other anions (i.e., phosphate, sulfate, silicate and tungstate) using model parameters obtained from the fitting of single ion adsorption envelopes. CD-MUSIC results strongly agree with the experimental adsorption envelopes of molybdate over the pH range from 3.5 to 10. Furthermore, CD-MUSIC prediction of the molybdate adsorption isotherm show a satisfactory fit of the experimental results. Modeling results suggest that the diprotonated monodentate complexes, FeOW(OH)(5)(-0.5) and FeOMo(OH)(5)(-0.5), were respectively the dominant complexes of adsorbed W and Mo on goethite 110 faces at low pH. The model suggests that Mo and W are retained mainly by the formation of monodentate complexes on the goethite surface. Our results indicate that surface complexation modeling may have applications in predicting competitive adsorption in more complex systems containing multiple competing ions.     

Modeling porosity reductions caused by mineral fouling in continuous-wall permeable reactive barriers

A study was conducted to assess key factors to include when modeling porosity reductions caused by mineral fouling in permeable reactive barriers (PRBs) containing granular zero valent iron. The public domain codes MODFLOW and RT3D were used and a geochemical algorithm was developed for RT3D to simulate geochemical reactions occurring in PRBs. Results of simulations conducted with the model show that the largest porosity reductions occur between the entrance and mid-plane of the PRB as a result of precipitation of carbonate minerals and that smaller porosity reductions occur between the mid-plane and exit face due to precipitation of ferrous hydroxide. These findings are consistent with field and laboratory observations, as well as modeling predictions made by others. Parametric studies were conducted to identify the most important variables to include in a model evaluating porosity reduction. These studies showed that three minerals (CaCO3, FeCO3, and Fe(OH)2 (am)) account for more than 99% of the porosity reductions that were predicted. The porosity reduction is sensitive to influent concentrations of HCO3-, Ca2+, CO3(2-), and dissolved oxygen, the anaerobic iron corrosion rate, and the rates of CaCO3 and FeCO3 formation. The predictions also show that porosity reductions in PRBs can be spatially variable and mineral forming ions penetrate deeper into the PRB as a result of flow heterogeneities, which reflects the balance between the rate of mass transport and geochemical reaction rates. Level of aquifer heterogeneity and the contrast in hydraulic conductivity between the aquifer and PRB are the most important hydraulic variables affecting porosity reduction. Spatial continuity of aquifer hydraulic conductivity is less significant.     

Inverse modeling of multicomponent reactive transport through single and dual porosity media

Compacted bentonite is foreseen as buffer material for high-level radioactive waste in deep geological repositories because it provides hydraulic isolation, chemical stability, and radionuclide sorption. A wide range of laboratory tests were performed within the framework of FEBEX (Full-scale Engineered Barrier EXperiment) project to characterize buffer properties and develop numerical models for FEBEX bentonite. Here we present inverse single and dual-continuum multicomponent reactive transport models of a long-term permeation test performed on a 2.5 cm long sample of FEBEX bentonite. Initial saline bentonite porewater was flushed with 5.5 pore volumes of fresh granitic water. Water flux and chemical composition of effluent waters were monitored during almost 4 years. The model accounts for solute advection and diffusion and geochemical reactions such as aqueous complexation, acid-base, cation exchange, protonation/deprotonation by surface complexation and dissolution/precipitation of calcite, chalcedony and gypsum. All of these processes are assumed at local equilibrium. Similar to previous studies of bentonite porewater chemistry on batch systems which attest the relevance of protonation/deprotonation on buffering pH, our results confirm that protonation/deprotonation is a key process in maintaining a stable pH under dynamic transport conditions. Breakthrough curves of reactive species are more sensitive to initial porewater concentration than to effective diffusion coefficient. Optimum estimates of initial porewater chemistry of saturated compacted FEBEX bentonite are obtained by solving the inverse problem of multicomponent reactive transport. While the single-continuum model reproduces the trends of measured data for most chemical species, it fails to match properly the long tails of most breakthrough curves. Such limitation is overcome by resorting to a dual-continuum reactive transport model.